scholarly journals Substituent Effects in the Crystal Packing of Derivatives of 4′-Phenyl-2,2′:6′,2″-Terpyridine

Crystals ◽  
2019 ◽  
Vol 9 (2) ◽  
pp. 110 ◽  
Author(s):  
Y. Klein ◽  
Alessandro Prescimone ◽  
Mariia Karpacheva ◽  
Edwin Constable ◽  
Catherine Housecroft
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Packing ◽  
Substituent Effects ◽  
Molecular Structures ◽  
Solution Nmr ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
Face To Face ◽  
Π Stacking ◽  
Derivatives Of

We report the preparation of a series of new 4′-substituted 2,2′:6′,2″-terpyridines: 4′-(3,5-dimethylphenyl)-2,2′:6′,2″-terpyridine (2), 4′-(3-fluoro-5-methylphenyl)-2,2′:6′,2″-terpyridine (3), 4′-(3,5-difluorophenyl)-2,2′:6′,2″-terpyridine (4), and 4′-(3,5- bis(trifluoromethyl)phenyl)-2,2′:6′,2″-terpyridine (5). The compounds have been characterized by mass spectrometry, solid-state IR spectroscopy and solution NMR and absorption spectroscopies. The single-crystal X-ray diffraction structures of 3, 5 and 6·EtOH (6 = 4′-(3,5-bis(tert-butyl)phenyl)-2,2′:6′,2″-terpyridine) have been elucidated. The molecular structures of the compounds are unexceptional. Since 3 and 5 crystallize without lattice solvent, we are able to understand the influence of introducing substituents in the 4′-phenyl ring and compare the packing in the structures with that of the previously reported 4′-phenyl-2,2′:6′,2″-terpyridine (1). On going from 1 to 3, face-to-face π-stacking of pairs of 3-fluoro-5-methylphenyl rings contributes to a change in packing from a herringbone assembly in 1 with no ring π-stacking to a layer-like packing. The latter arises through a combination of π-stacking of aromatic rings and N…H–C hydrogen bonding. On going from 3 to 5, N…H–C and F…H–C hydrogen-bonding is dominant, supplemented by π-stacking interactions between pairs of pyridine rings. A comparison of the packing of molecules of 6 with that in 1, 3 and 5 is difficult because of the incorporation of solvent in 6·EtOH.

Crystal structures of dihydroquercetin 3-acetate and dihydroquercetin 3,3'4',7-tetraacetate: hydrogen bonding in 5-hydroxyflavanones

1999 ◽  
Vol 77 (8) ◽  
pp. 1436-1443 ◽  
Author(s):  
Eberhard Kiehlmann ◽  
Kumar Biradha ◽  
Konstantin V Domasevitch ◽  
Michael J Zaworotko
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Single Crystal ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Heterocyclic Ring ◽  
Molecular Structures ◽  
Crystal Data ◽  
Aromatic Rings ◽  
X Ray

The molecular structures of dihydroquercetin 3-acetate 3 and dihydroquercetin 3,3',4',7-tetraacetate 4 were determined by single crystal X-ray analysis. Comparison of their crystal data with those of 16 known 5-hydroxyflavanones shows intramolecular O(5)-H···O(4)=C hydrogen bonding, preference for nearly perpendicular orientation of the two aromatic rings and preferred sofa conformation of the heterocyclic ring. The major stabilizing force in the crystal packing pattern of 3 is intermolecular hydrogen bonding.Key words: crystal structure, dihydroquercetin, flavanones, hydrogen bonding.

Substituent Effects and Structure in Substituted Dibenzonaphthyrones

1985 ◽  
Vol 38 (1) ◽  
pp. 97
Author(s):  
H Becker ◽  
CL Raston ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Double Bond ◽  
Substituent Effects ◽  
Molecular Geometry ◽  
Molecular Structures ◽  
The Other ◽  
Carbonyl Groups ◽  
X Ray Diffraction ◽  
Aromatic Rings ◽  
X Ray ◽  
Crystal And Molecular Structures

The crystal and molecular structures of [1]benzopyrano[4,3- c][1]benzopyran-5,11-done (dibenzo-naphthyrone) and three of its symmetrically tetrasubstituted derivatives have been determined by single-crystal X-ray diffraction methods. Only the tetra-t-butyl-substituted dibenzonaphthyrone was found to deviate significantly from planarity by having the two carbonyl groups folded and 'syn'-oriented relative to the plane of the connecting ethylene double bond. The dihedral angle between the two aromatic rings was found to be 25. The molecular geometry of all the other dibenzo-naphthyrones in their crystalline states is characterized by planarity, and their structures are centrosymmetric.

scholarly journals Manipulating the Conformation of 3,2′:6′,3″-Terpyridine in [Cu2(μ-OAc)4(3,2′:6′,3″-tpy)]n 1D-Polymers

Chemistry ◽  
2021 ◽  
Vol 3 (1) ◽  
pp. 182-198
Author(s):  
Dalila Rocco ◽  
Samantha Novak ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Single Crystal ◽  
Crystal Structures ◽  
Metal Binding ◽  
Polymer Chains ◽  
X Ray Diffraction ◽  
Face To Face ◽  
Single Crystal Structures ◽  
Π Stacking ◽  
Metal Binding Domain ◽  
Packing Interactions

We report the preparation and characterization of 4′-([1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (1), 4′-(4′-fluoro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (2), 4′-(4′-chloro-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (3), 4′-(4′-bromo-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (4), and 4′-(4′-methyl-[1,1′-biphenyl]-4-yl)-3,2′:6′,3″-terpyridine (5), and their reactions with copper(II) acetate. Single-crystal structures of the [Cu2(μ-OAc)4L]n 1D-coordination polymers with L = 1–5 have been determined, and powder X-ray diffraction confirms that the single crystal structures are representative of the bulk samples. [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n are isostructural, and zigzag polymer chains are present which engage in π-stacking interactions between [1,1′-biphenyl]pyridine units. 1D-chains nest into one another to give 2D-sheets; replacing the peripheral H in 1 by an F substituent in 2 has no effect on the solid-state structure, indicating that bifurcated contacts (H...H for 1 or H...F for 2) are only secondary packing interactions. Upon going from [Cu2(μ-OAc)4(1)]n and [Cu2(μ-OAc)4(2)]n to [Cu2(μ-OAc)4(3)]n, [Cu2(μ-OAc)4(4)]n, and [Cu2(μ-OAc)4(5)]n·nMeOH, the increased steric demands of the Cl, Br, or Me substituent induces a switch in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and a concomitant change in dominant packing interactions to py–py and py–biphenyl face-to-face π-stacking. The study underlines how the 3,2′:6′,3″-tpy domain can adapt to different steric demands of substituents through its conformational flexibility.

Structural and spectroscopic studies of transition metal nitrite complexes. V. Crystal structures and spectra of trans-Tetrakis(pyridine)dinitritonickel(II)-pyridine (1/2), trans-Tetrakis(4-methylpyridine)dinitritonickel(II) and trans-Tetrakis(pyrazole)-dinitritonickel(II)

1981 ◽  
Vol 34 (10) ◽  
pp. 2095 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
BW Skelton ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Transition Metal ◽  
Crystal Structures ◽  
Electronic Spectra ◽  
Spectroscopic Studies ◽  
Molecular Structures ◽  
Aromatic Rings ◽  
Paddle Wheel ◽  
Crystal And Molecular Structures ◽  
Infrared Frequencies

The crystal and molecular structures of the compounds [Ni(py)4(ONO)2],2py, [Ni(γmpy),(ONO)2] and [Ni(prz)4(ONO)2] are reported.�All three are trans nitrito complexes, the pyridine (py) compound containing two pyridine molecules of solvation. The aromatic rings in the first two complexes adopt 'paddle wheel' conformations with pitch angles varying between 40 and 70�. The nitrite ions are positioned so as to minimize repulsive interactions with the amines, and it seems likely that these groups bond through oxygen rather than nitrogen because this allows a lesser degree of interligand steric interference. The amine rings in [Ni(prz)4(ONO)2] are orthogonal to the plane containing the nickel and coordinated pyrazole nitrogen atoms; the nitrito groups are disordered between two inequivalent positions, each of which involves hydrogen bonding with the pyrazole NH groups. The nitrite infrared frequencies are similar to those observed for other nickel(II) nitrito complexes except that the antisymmetric NO stretching mode of one of the groups in the pyrazole complex is much lower in energy than expected, being in the range normally associated with a nitrogen-bonded or chelated nitrite group. It is suggested that this deviation may be caused by the hydrogen bonding in the complex. The electronic spectra of the compounds yield 10Dq values of 9100 and 8500 cm-1 for the nitrite ligands in [Ni(py)4(ONO)2] and Ni(prz)4(ONO)2], respectively, placing the nitrito group towards the weaker end of the spectro-chemical series.

Beziehungen zwischen Rotationsisomerie, Wasserstoffbrücken-Bindung und Substituenteneffekten der organischen Chemie / Relations between Rotational Isomerism, Hydrogen Bonding, and Substituent Effects in Organic Chemistry

1972 ◽  
Vol 27 (6) ◽  
pp. 663-674 ◽  
Author(s):  
Gotthard H. Krause ◽  
Herbert Hoyer
Keyword(s):  
Hydrogen Bonding ◽  
Substituent Effects ◽  
Intramolecular Hydrogen Bonding ◽  
Rotational Isomerism ◽  
Proton Acceptor ◽  
Single Bond ◽  
Free Enthalpy ◽  
Acceptor Group ◽  
Intramolecular Hydrogen ◽  
Derivatives Of

The change of free enthalpy involved in intramolecular hydrogen bonding is smaller if the proton acceptor group can rotate round a single bond, as compared to proton acceptor groups which are fixed in a position optimal for hydrogen bonding. Also, the free enthalpy change is altered when the rotation of the proton acceptor is sterically restricted. This is demonstrated by comparing the absorptions of carbonyl stretching vibrations in the infrared spectra of certain compounds showing rotational isomerism. In the present study derivatives of 5-hydroxy-2,2-dimethyl-6-carbomethoxychromanone- (4), 3-nitrosalicylaldehyde and 3-nitro-2-hydroxy-acetophenones substituted in the position 5 and 6 are examined.

Study on Novel Structure of Praseodymium Complex, C5H13O11Pr

2013 ◽  
Vol 834-836 ◽  
pp. 515-518
Author(s):  
Hai Xing Liu ◽  
Qing Liu ◽  
Ting Ting Huang ◽  
Yang Xu ◽  
Lin Tong Wang ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Single Crystal ◽  
Hydrothermal Reaction ◽  
Crystal Packing ◽  
X Ray Diffraction ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Novel Structure ◽  
Praseodymium Complex

A novel praseodymium complex C5H13O11Pr has been synthesized from hydrothermal reaction and the crystal structure has been determined by means of single-crystal X-ray diffraction. The Pr1 atom is nine coordinated by nine O atoms. The crystal packing is stabilized by O-H...O hydrogen bonding interactions.

5-Nitrosalicylaldehyde (2-hydroxybenzoyl)hydrazone

2006 ◽  
Vol 62 (7) ◽  
pp. o3026-o3027 ◽  
Author(s):  
Hong-Mei Xu ◽  
Shi-Xiong Liu
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Crystal Packing ◽  
Dihedral Angles ◽  
Stacking Interactions ◽  
Aromatic Rings ◽  
Compound C ◽  
Π Stacking

The molecule of the title compound, C14H11N3O5, is approximately planar, the dihedral angles between the two aromatic rings being 4.63 (7)°. O—H...N, N—H...O and O—H...O hydrogen bonds and π–π stacking interactions help to consolidate the crystal packing.

β-Hydroxydithiozimtsäurederivate als Liganden. Synthese und Charakterisierung neuartiger 1,1-Ethendithiolato- und O,S-Chelatkomplexe / Derivatives of β -Hydroxydithiocinnamic Acids as Ligands. Syntheses and Characterisation of Novel 1,1-Ethenedithiolato and O,S-Chelate Complexes

2007 ◽  
Vol 62 (3) ◽  
pp. 475-482 ◽  
Author(s):  
Karsten Schubert ◽  
Helmar Görls ◽  
Wolfgang Weigand
Keyword(s):  
Bidentate Ligand ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
H Nmr ◽  
Hexyl Ester ◽  
Elemental Analyses ◽  
Derivatives Of ◽  
C Nmr

Starting from 4-bromoacetophenone 1, the 4-bromo-β -hydroxydithiocinnamic acid 2 and the 4-bromo-β -hydroxydithiocinnamic acid hexyl ester 3 were prepared using carbon disulfide and potassium-tert-butylate as a base. Acting as a ligand, the acid gives 1,1-ethenedithiolato complexes with (Ph3P)2Pt(II) (4a), (Et3P)2Pt(II) (4b), dppePt(II) (4c), (Ph3P)2Pd(II) (4d), dppePd(II) (4e), and dppeNi(II) (4f). In contrast to the acid, the deprotonated ester 3 forms a monoanionic bidentate ligand. [O,S] Complexes of Pt(II) (5a), Pd(II) (5b) and Ni(II) (5c) were obtained. All complexes have been fully characterised using 1H NMR, 13C NMR and 31P NMR spectroscopy, mass spectrometry, infrared spectroscopy and elemental analyses. The molecular structures of the complexes 4b and 5a - 5c were determined by X-ray diffraction analyses.

Aminkomplexe des Goldes, Teil 10: Gold(I)-thiocyanat-Komplexe mit Tetrahydrothiophen, Dimethylsulfid, Ammoniak, Aminen und Azaaromatena

2018 ◽  
Vol 73 (2) ◽  
pp. 125-147 ◽  
Author(s):  
Mark Strey ◽  
Cindy Döring ◽  
Peter G. Jones
Keyword(s):  
Dimethyl Sulfide ◽  
Crystal Packing ◽  
Molecular Structures ◽  
Secondary Amines ◽  
X Ray ◽  
Anions And Cations ◽  
Derivatives Of ◽  
Aurophilic Interactions ◽  
Ray Methods ◽  
Alternating Chain

AbstractThe reaction of (tht)AuCl (tht=tetrahydrothiophene) with KSCN leads to a mixture of gold(I) thiocyanate AuSCN and [(tht)2Au]+ [Au(SCN)2]−1. The compounds were separated and the X-ray structure of 1 confirmed as an alternating chain of anions and cations linked by aurophilic contacts. Either pure AuSCN or the mixture was used to synthesize further derivatives of AuSCN, all of which were investigated by X-ray methods. Most products were of limited stability when removed from their mother liquor. The dimethyl sulfide derivative 2 is molecular, (Me2S)AuSCN; the ammonia derivative 3 is ionic, [(NH3)2Au]+ [Au(SCN)2]−. The reaction with 2,2-bipyridyl leads (presumably by involvement of the solvent or of atmospheric moisture) to [bipy-H]+ [Au(SCN)2]−13. All other products involve amines or azaaromatics as ligands L. The primary amine tert-butylamine forms an ionic product [L2Au]+ (SCN)−4. The secondary amines piperidine and dibenzylamine lead to molecular structures LAuSCN (5 and 6), whereas pyridine-based azaaromatics lead to ionic products [L2Au]+ [Au(SCN)2]− with L=2-, 3- or 4-picoline (7–9), 2,4-, 3,4- or 3,5-lutidine (10–12). The 3,4-lutidine derivative 11 forms two polymorphs that tend to form mixed crystals. The dominant features of the crystal packing for 7–12 are short aurophilic interactions.

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